Acid-base and complexing properties of some δ-hydroxyalkenylphosphine oxides

Article abstract of DOI:10.1134/S1070363213060145

Four new compounds, asymmetrical phosphine oxides containing 2-hydroxyphenylethenyl fragment in cis-orientation with respect to the phosphine oxide: dibutyl-, diphenyl-, dibenzyl-, and dinaphthyl-2-(2-hydroxy-5- chlorophenyl)-2-phenyl-ethenylphospnine oxi

Full text of DOI:10.1134/S1070363213060145

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 6, pp. 1087–1093. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.F. Mironov, Yu.I. Sal’nikov, G.A. Boos, D.A. Tatarinov, A.P. Nikitin, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 6, pp. 956–962.
Acid-Base and Complexing Properties
of Some δ-Hydroxyalkenylphosphine Oxides
V. F. Mironova,b, Yu. I. Sal’nikova, G. A. Boosa,
D. A. Tatarinova,b, and A. P. Nikitinb
a Kazan State University, ul. Kremlevskaya 18, Kazan, Tatarstan, 420008 Russia
e-mail: mironov@iopc.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received May 15, 2012
Abstract—Four new compounds, asymmetrical phosphine oxides containing 2-hydroxyphenylethenyl
fragment in cis-orientation with respect to the phosphine oxide: dibutyl-, diphenyl-, dibenzyl-, and dinaphthyl-
2-(2-hydroxy-5-chlorophenyl)-2-phenyl-ethenylphospnine oxides, have been studied in aqueous ethanol (80 vol %
of EtOH) by means of potentiometry and spectrophotometry at 25±0.1°C, and their acid-base and complexing
properties estimated.
DOI: 10.1134/S1070363213060145
The interest to organophosphorus compounds
originates from their structural diversity and unique
combination of properties important for applied as well
as fundamental studies. Among derivatives of four-
coordinated phosphorus, phosphine oxides are of
particular importance. They possess perfect extraction
(complexing) properties towards rare, rare-earth, and
other nonferrous metal ions; and they are precursors of
phosphines that are applied as ligands in metal
complex catalysis.
oxide (Ic), the method described and patented in [3]
was used. The corresponding dibutyl Ia and dinaphthyl
Id derivatives were prepared by the same approach for
the first time. All four compounds are hydroxy-
phosphine oxides. Their protolytic properties and
behavior of some of them in the presence of iron(III),
copper(II), and nickel(II) were studied.
Phosphine oxides Ia–Id were synthesized starting
from
2,6-dichloro-4-phenylbenzo[e][1,2]oxaphos-
phorine 2-oxide (II), phosphorus-containing hetero-
cycle containing a P–C bond, which was in turn
prepared via reaction of 2,2,2-trichloro-2-benzo-1,3,2-
dioxaphosphole with phenylacethylene [4]. Reactions
of oxaphosphorine oxide (II) with twofold excess of
the corresponding organomagnesium compounds in
ether under mild conditions lead selectively and with
high yield (>90%) to target compounds (I). Structures
of the compounds thus obtained were proved by mass
spectrometry, NMR spectroscopy (31P, 1H, 13C), and IR
spectroscopy.
Commonly known organometalic chemistry
methods for preparation of phosphorus-containing
complex ligands are not selective and often require the
use of hard-to-get chemicals [1, 2]. Furthermore, these
methods are not applicable to substrates containing
other active functional groups. It is noteworthy that
almost all these methods start with phosphinic halides
or alkali metal dialkylphosphides as precursors; as
these compounds are very reactive, inert atmosphere is
required. Recently, we have developed a new approach
to the preparation of substituted alkenylphosphine
oxides [3] based on reaction of readily available cyclic
phosphorus esters with organomagnesium compounds.
Phosphoryl and hydroxy groups in phosphine
oxides are in cis-orientation, which is determined by
the structure of oxaphosphorine cycle of the precursor
(oxaphosphorine double bond is not affected in the
reaction with Grignard reagents).
In this work, four new compounds were studied.
For preparation of diphenyl- (Ib) and dibenzyl-2-(2-
hydroxy-5-chlorophenyl)-2-phenylethenylphosphine
1087

1088
MIRONOV et al.
8
5
OH
8a
4a
O
P
7
R
R
O
O
(1) RMgX
P
Cl
Cl
6
3
(2) H2O, H+
4
9
Cl
10
Ph
12
11
13
I
II
21
18
22
17
14
15
20
19
13−16
(Id).
R = Bu (Ia), Ph (Ib), PhCH2 (Ic),
16
Aqueous ethanol (80 vol % EtOH) turned out to be
a suitable solvent for studies of protolytic and
complexing properties of compounds Ia, Ib. In cases
of Ic, Id, due to their poor solubility (<2×10–3 M), it
was not possible to achieve the concentration desired
for potentiometric measurements. Compound Ia, as
well as Ib, was not titrated by acid. The shape of the
titration curves with no leap in alkaline pH range leads
to the assumption that the studed compounds were
neutral (neither basic nor acidic).
(Fig. 1, curve 1) there was a well defined maximum at
the wavelength λ = 525 nm, ε525 = 590 l mol–1 cm–1.
This fact clearly proved the interaction of Ia with iron(III).
The solution of Ib in the presence of iron(III) under
the same conditions (pH = 2.18) was also violet.
However, the absorption maximum was shifted to the
higher wavelength (λmax = 565 nm), and the absorption
intensity was somewhat smaller, ε565 = 420 l mol–1 cm–1
(Fig. 2, curve 3).
Solutions of compounds Ic, Id in the presence of
iron(III) were yellow, as well as iron(III) solution
itself. Visible absorption spectra of all these solutions
were identical. As an example, there was no absorption
maximum at 525 nm in the spectrum of Ic solution in
the presence of iron(III) (Fig. 1, curve 2). The molar
The complexing ability towards iron(III) in aqueous
ethanol (80 vol % EtOH) was most clearly revealed in
compounds Ia, Ib, especially, in the case of Ia. Upon
addition of iron(III) to the Ia solution, it turned
intensively violet (pH ≈ 2). In the absorption spectrum
absorption coefficient of the Ic/iron(III) mixture ε525
=
A
110 l mol–1 cm–1 was higher than that of the solvated
iron(III), 24 l mol–1 cm–1 (Fig. 2, curves 1, 2).
The quantitative analysis of the spectroscopic data
was performed for the iron(III)–compound Ia system.
The optical density at wavelength λ = 525 nm was
measured for two series of samples prepared at
constant concentration of the complexing agent
(8.48×10–4 or 1.696×10–3 M) and variable concentra-
tion of ligand (Ia), its highest concentration being
limited by its solubility. The desired acidity of the
medium (pH ≈ 2.0) was adjusted by nitric acid.
Experimental data are collected in Fig. 3.
Compounds Ia–Id studied in this work contained
the p-chlorophenyl substituent. It was assumed that the
HL compound Ia was coordinated in the phenolate
form L, similar Fe(III) interaction with p-chloro-
phenol [10, 11].
λ, nm
Fig. 1. Absorption spectra of aqueous ethanol solutions of
(1) Ia and (2) Ic in the presence of iron(III). cFe(III), M: (1)
5.94×10–3, (2) 4.24×10–3; cIa,Ic, M: 1.2×10–2 (Ia), <2×10–3
(Ic); pH 2.0; ε525, l mol–1 cm–1: (1) 592, (2) 110.
The combined analysis of the data for both series
revealed that equilibria defined by Eq. (1) were
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ACID-BASE AND COMPLEXING PROPERTIES
1089
A
A
λ, nm
Fig. 2. Absorption spectra of aqueous ethanol solutions of
(1, 2) iron(III) and of Ib in the presence of (3) iron(III).
cIа/cFe(III)
c
Fe(III), M: (1) 8.48×10–4, (2) 1.696×10–3, (3) 2.0352×10–3;
Fig. 3. Dependence of optical density A on cIa/cFe(III)
EtOH = 80 vol % ; cFe(III), M: (1) 8.48×10–4, (2) 1.696×10–3;
pH 2.08–2.14; A1 lim 0.516, A2 lim 1.021; λ = 525 nm.
.
cIb 3.99×10–3 M; pH: (1) 2.16, (2) 2.14, (3) 2.18; ε525
l mol–1 cm–1: (1) 24.8, (2) 23.6, (3) ε565 420.
,
c
established in aqueous ethanol solution of Ia in the
presence of iron(III).
According to [13], the sensitivity of the reaction of
iron(III) with phenol increases (accompanied by the
decrease in the selectivity) upon introduction in the o-
position of donor groups, like C(O)R, OH, and some
others. The presence of a carbonyl group in the o-
position with respect to the hydroxy group stipulates
the violet color of complexes formed in the presence of
iron(III), for instance, of salicylate ones [14]. The
complex formation is favored by reduced hydrolysis of
Fe3+ + nHL ⇄ [FeLn]3–n + nH+.
(1)
Here n = 1, 2. In solution, complexes of 1:1 and 1:2
compositions, [FeL]2+ and [FeL2]+, coexisted. The
highest fractions for both of them were relatively small
(Fig. 4). For the first complex, αmax = 0.55 in both
series, for the second complex αmax = 0.34 at highest
possible ligand concentration (3.6×10–3 M under
conditions of the experiment). Quantitative character-
istics of the complex formation process are collected in
the table that contains equilibrium constants, highest
complex fractions (αmax), and the corresponding molar
absorption coefficients (ε) for both complexes.
α
Additionally, potentiometric titration of Ia and Ib
solutions containing iron(III) was performed, at the
complexing agent to ligand ratio of 2:1 (Fig. 5). The
solutions, initially violet, in the course of titration
changed to brown, and then became turbid, likely due
to the formation of iron(III) basic salts or hydroxide.
At the end of titration, the samples contained a plenty
of iron(III) hydroxide precipitate. Thus, violet
complexes existed in acidic medium (pH ≈ 2.0) but
were readily decomposed by alkali {solubility product
is 3.8×10–38 for [Fe(OH)3] in aqueous solution [12]}.
log cIа
It is well known that for a colored complex with
iron(III) to exist, it is essential that there is at least one
phenol hydroxy group in the organic compound.
Fig. 4. Fractional distribution of complex forms in the
system iron(III)–Ia. cFe(III) 8.48×10–4 M; (1) Fe(III),
(2) [FeL]2+, (3) [FeL2]+.
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MIRONOV et al.
Equilibrium constants in complexing reactions between
iron(III) and Ia in aqueous ethanol solution (80 vol %
EtOH). R = 3.0%
not be that high. Indeed, for the complex of iron(III)
and p-chlorophenol violet coloring is observed (λmax
=
562 nm, εmax = 27.2 l mol–1 cm–1). The coloring is
stable within one hour, but disappears at high ethanol
concentration [10].
Equilibrium
1, n = 1
log K
ε, l mol–1 cm–1 (λ 525 nm)
αmax
0.55
0.34
1.07±0.03
1.36±0.12
643
872
It is known that isolated chelate cycles with more
than six atoms in the cycle are unstable. However,
when accompanied with simultaneous formation of 5-
or 6-membered chelate cycles, the chelate cycles of
any size may be stabilized [13]. Such complementary
chelate cycles are absent in the structure of the studied
complex. The large cycle may have been stabilized by
the rigidity of the aromatic structural fragments. Note
that the formation of an eight-membered ring in the
polymeric lantanide(III) complexes [Ln(NO3)3Z]ROH
with phosphine oxide Z {CH3C[CH2P(O)Ph2]3}, ROH
being methanol or ethanol, was described in [16].
1, n = 2
the cation in strongly acidiс medium or in nonaqueous
solvent [15].
The appearance of violet coloring (ε525
=
590 l mol–1 cm–1) upon addition of iron(III) to aqueous
ethanol (80 vol % EtOH) solution of dibutyl-2-(2-
hydroxy-5-chlorophenyl)-2-phenylethenylphosphine
oxide (Ia) presumed that a complex with bidentate
coordination and eight-membered ring was formed.
Phenolate and phosphoryl groups participated in the
coordination. For the 1:1 complex, the following
scheme corresponds to the assumed coordination type.
Ph
Ph
O
P
Fe3+
Bu
Bu
P
Ln3+
O
O
Bu
P
O
O
P
Bu
Ph
Ph
Cl
+3Ln
Ph
As far as copper(II) is concerned, a considerable
acidification of copper(II) solution in the presence of
Ia (pH 4.41 and 3.61, correspondingly), as well as the
changes in the absorption spectra as compared with
that of solvated copper, show the interaction of the
studied system components, accompanied with protons
release. In the solvated copper(II) spectrum, no new
bands appeared upon addition of Ia, whereas the
intensity of the present band only slightly increased. In
this case, the formation of chelate complex is also
possible, like in the case of iron(III).
Vacant sites in the complexing agent coordination
sphere are occupied by the solvent molecules.
If monodentate ligand coordination was realized
(like with p-chlorophenol and other common phenols),
the intensity of the formed complex absorption could
pH
Spectra of copper-containing solutions of
compounds Ia (curve 1) and Ib (curve 4) are shown in
Fig. 6 [ligand:copper(II) = 2:1].
Higher concentration of Ib could not be achieved
due to its poor solubility. Visible light absorption of
both systems was similar (ε800 = 23.2 l mol–1 cm–1 and
24.2 l mol–1 cm–1, correspondingly). However, the
limited solubility of Ib impedes the studies of its
complexing with copper(II) in solution, as the desired
ligand concentration could not be attained.
VNaOH, ml
Fig. 5. Potentiometric titration curves of aqueous ethanol
solutions of (1) Ia and (2) Ib in the presence of iron(III).
cEtOH = 80 vol %, cIa = 1.2×10–2 M, cIb = 3.99×10–3 M;
Molar absorption of both compounds solutions in
the presence of nickel(II) were even lower than in case
of copper(II). Their values were close to those of
nickel(II) solvates. Note that absorption bands of
c
Fe(III), M: (1) 5.94×10–3, (2) 2.04×10–3; cNaOH, M: (1) 2.385×
10–2, (2) 7.95×10–3.
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ACID-BASE AND COMPLEXING PROPERTIES
1091
nickel(II) aqua complex are of low intensity: λ1 = 395
A
nm, ε = 5 l mol–1 cm–1; λ2 = 658 nm, ε = 2 l mol–1 cm–1;
λ3 = 724 nm, ε = 2 l mol–1 cm–1 [17].
EXPERIMENTAL
Electron absorption spectra were recorded using
spectrophotometers Lambda 35 101N6112101
(Perkin–Elmer UV WinLab) and SPEKOL 11, in
quartz cell (optical path length = 1 cm), with pure
1
solvent as a reference. Н, 31Р, and 31Р–{1Н} NMR
spectra were collected using Bruker MSL-400 (1Н
400.0 MHz; 31Р 162.0 MHz) and Avance 600 (1H
600.0 MHz) instruments in DMSO-d6 (30°С) and
CDCl3 (25°С), reference Me4Si or H3PO4. Residual
solvent proton signals were also used as internal
reference (1Н). IR spectra of suspensions in mineral oil
were recorded using UR-20 and Bruker Vector-22
instruments. Electron impact mass spectra were
detected using TRACE MS Finnigan MAT or МKh-
1310 with high-precision m/z determination, coupled
with the CM-4 computer. The ionizing electrons
energy was 70 eV, electrons source temperature was
up to 250°С. The system of direct substance injection
into the ion source was used. Mass spectra were
analyzed with Xcalibur program.
λ, nm
Fig. 6. Absorption spectra of aqueous ethanol solutions of
Ia, Ib in the presence of (1, 4) copper(II) and (2, 3) nickel(II).
cIa 1.6×10–2, cIb 4×10–3; cCu(II), M: (1) 7.75×10–3, (4)
1.94×10–3; cNi(II), M: (2) 8.78×10–3, (3) 2.20×10–3; pH: (1) 3.20,
(2) 3.61, (3) 5.36, (4) 4.14; ε800, l mol–1 cm–1: (1) 23.2,
(4) 24.2, ε655, l mol–1 cm–1: (2) 6.6, (3) 11.2.
towards HCl solutions of known concentration [5],
after incubation for at least one day in the corres-
ponding solvent. Solutions of Ia–Id were prepared
from precisely weighed specimens. Anhydrous ethanol
was prepared according to [6]. Solutions of carbonate-
free sodium hydroxide, hydrochloric acid, nitrates of
nickel(II), copper(II), and iron(III) were prepared from
the corresponding chemicals of the chemically pure
grade. The solutions concentration was determined by
volumetric analysis. The same concentration of
organic solvent was maintained in titrants as well as in
titrates. Ionic strength of the solutions was solely due
to their components, as base electrolyte addition could
reduce studied compounds solubility, or influence
association in solution. The titration was performed
under argon stream. Titrated solutions were stirred
using a magnetic stirrer. In the solutions prepared for
titration, reproducible values of glass electrode potential
were established within 15–20 min; in the course of
the titration, this period was reduced to 3–5 min.
Electron absorption spectra were analyzed with
CPESSP program [7]. Reliability of the selected
models was characterized with F and R factors [8, 9].
F = ΣNk+1 [(QKexp – QKtheor)WК]2,
F = Fmin/(N – 2n).
In these equations, QKexp is a property of the
solution measured in the k experiment, QKtheor is its
theoretical analog, N is the number of experimental
points, WK is a normalizing factor, or statistical weight,
n is the number of varied parameters. For spectro-
photometric experiment, F = Fmin/(N – 2n) (varied
parameters are equilibrium constants and molar
absorptivities). Average deviation of theoretical data
from experimental ones, R [9] was less than 0.05 (5%).
Protolytic and complexing properties of the
compounds under study in aqueous ethanol (80 vol %
EtOH) were estimated from potentiometric and
spectrophotometric data. Measurements were per-
formed in a temperature-controlled chamber at 298 K.
The pH of solutions was measured with a MV88
PRAZISIONS-LABOR-pH-MESSGERAT instrument.
Glass electrode (ELS-63-07) was used as a working
electrode, and saturated silver chloride electrode was
used as a reference one. Glass electrode was calibrated
Dibutyl-2-(2-hydroxy-5-chlorophenyl)-2-phenyl-
ethenylphosphine oxide (Ia). Grignard reagent was
obtained via a standard procedure from 3.7 g
(0.15417 mol) of magnesium and 16.6 ml (21.15 g,
0.1542 mol) of bromobutane in 15 ml of diethyl ether.
The solution containing 20 g (0.0643 mol) of oxa-
phosphorine oxide (II) in 20 ml of benzene was added
dropwise to the Grignard reagent, and the mixture was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 6 2013

1092
MIRONOV et al.
(100.6 MHz, DMSO-d6, 45°C), δC, ppm (J, Hz):
heated to boiling for 0.5 h. Then the solution was
cooled and hydrolyzed with distilled water and 28.4 ml
of hydrochloric acid. The organic and aqueous layers
were separated. The organic phase was washed with
distilled water; then the solvents were distilled off
under a reduced pressure. 20.4 g (89.5%) of (Ia) was
obtained in the form of yellowish viscous oil-like
substance. IR, ν, cm–1: 766 (P–C), 1128 (P=O), 1572
(C=CAr), 1588 (C=CAr), 3363 (OH). 1Н NMR
(600 MHz, CDCl3), δ, ppm (J, Hz): 0.9 t (6Н, СН3,
3JНСCH 7.3), 1.38 m (4Н, СН2), 1.49 m (4Н, СН2),
1.55–1.8 m (4Н, PСН2, АВ of АВМХ2), 6.4 d (1H,
1
1
122.32 d.d (d) (PC3, JPC 103.6, JHC 153.0), 155.35
2
3
m.d (d) (C4, JPC 1.2), 126.85 m (d) (C4а, JРC 7.0–8.0,
partially overlap with С20 signal), 129.93 d.d (s) (C5,
3
2
1JHC 170.8, JHC 5.7–6.0), 121.47 d.d.d (s) (C6, JHC
3.9–4.0, 2JHC 3.9–4.0, 3JHC 12.4), 128.80 br.d.d (s) (C7,
1JHC 218.8, 3JHC 5.3–5.6), 116.82 d (s) (C8, 1JHC 161.1),
153.70 br.d.d (s) (C8а, 3JHC 8.3, 3JHC 8.3), 140.21 m (d)
(C9, JPC 17.1), 129.03 d.m (s) (C10, JHC 160.6),
3
1
128.47 br.d.d (s) (C11, JHC 161.3, JHC 5.48–5.74),
1
2
129.19 d.d (d) (C12, JHC 161.3), 129.98 d.m (d) (PC13,
1
1JPC 103.2), 132.58 br.d.m (d) (C14, JHC 162.2, JPC
1
2
РСН, JРH 19.1), 6.91 d (1H, Н5, JНH 2.6), 7.1 d (1H,
10.3, JHC 9.5), 124.84 br.d.d (d) (C15, JPC 13.7, JHC
2
4
3
3
1
3
3
4
1
3
Н8, JНH 8.4), 7.27 br.d.d (1H, Н7, JНH 8.4, JНH 2.6),
7.3–7.4 (5H, Н10, Н11, Н12). 13C NMR (100.6 MHz,
CDCl3, 25°C), δC, ppm (J, Hz) (hereinafter view of the
signal in the 13C–{1H} NMR spectrum is given in
162.9), 132.72 br.d.d.d (s) (C16, JHC 164.7, JHC 5.8–
6.0, JHC 5.0–5.2), 132.70 d.m (d) (C17, JPC 8.6),
3
3
126.82 br.d.d.d (C18, JHC 160.1, JHC 5.8–6.0, JHC
1
3
3
5.0–5.2), 126.30 d.d (s) (C19, JHC 161.2, JHC 8.4),
1
3
parentheses): 119.30 br.d.d (d) (C3, JPC 90.4, JHC
126.86 d.d (s) (C20, JHC 161.9, JHC 8.9), 126.79
1
1
1
3
150.8), 154.92 m (d) (C4, JPC 2.5), 127.28 m (br.d)
br.d.d.d (C21, JHC 160.0, JHC 8.0–8.2, JPC 4.8),
2
1
3
3
(C4а, 3JPC 5.6, 3JHC 6.9), 129.26 d.d (s) (C5, 1JHC 165.3,
3JHC 5.8), 123.15 d.d.d (s) (C6, 3JHC 11.3, 2JHC 3.8, 2JHC
3.8), 129.49 d.d (s) (C7, 3JHC 5.8, 1JHC 160.5), 118.48 d
133.49 m (d) (C22, JPC 9.2). 31Р–{1H} NMR (DMSO-
2
d6): δР 25.4 ppm. EI MS, m/z: 530 [М]+•
(C34H24Cl35O2P), 495 [М – Cl], 478 [М – Cl – OH],
453 [М – C6H5], 438, 423, 409, 395, 383, 368 [М –
C10H7 – Cl], 302 [C20H15OP], 253, 215, 173, 128, 97,
83, 57, 55, 43. Found, %: C 76.85; H 4.60; P 5.83.
C34H24ClO2P. Calculated, %: C 76.91; H 4.56; 5.86.
(s) (C8, JHC 162.8), 153.78 d.d.d (s), (C8а, JHC 9.3,
1
3
3JHC 8.5, JHC 1.7), 139.95 m (d) (C9, JPC 15.5, JHC
2
3
3
7.2–8.1, JHC 6.6), 126.76 br.d.m (s) (C10, JHC 158.9,
3
1
3JHC 6.2–6.9), 127.98 br.d.d (s) (C11, JHC 160.5, JHC
1
3
7.3–7.5), 129.01 d.t (s) (C12, JHC 161.4, JHC 7.4),
1
3
ACKNOWLEDGMENTS
28.30 t.d.m (d) (PCH213, JPC 69.5, JHC 129.6), 23.15
1
1
t.m (br.s) (CH214, JHC 128.6), 23.65 t.d.m (d) (CH2
,
1
15
This work was financially supported by grant of the
President of the Russian Federation for the State
support of young Russian scientists – candidates of
science (project MK-1172.2010.3).
1JHC 123.8, JPC 15.0), 13.58 comp. m (s) (CH316, JHC
3
1
125.0, JHC 4.0–4.2). 31Р–{1H} NMR (DMSO-d6): δР
3
41.3 ppm. EI MS, m/z: 390 [М]+• (C22H28Cl35O2P), 373
[М – ОН], 355 [М – Cl], 333 [М – C4H9], 317 [М –
C4H9 – OH], 290 [М – C4H9 – C3H7], 258 [М – 2C4H9 –
OH], 230 [C14H11ClO], 228 [C14H9ClO], 214, 176, 162
[C8H19OP], 132, 119, 91, 106, 77, 63, 29. Found, %: C
67.63; H 7.16; P 8.37. C22H28ClO2P. Calculated, %: C
67.60; H 7.22; P 7.92.
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Gubaidullin, A.T., Petrov, R.R., Shtyrlina, A.A.,
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Il’yasov, A.V., Russ. J. Gen. Chem., 1998, vol. 68,
no. 9, pp. 1414–1442.
Dinaphthyl-2-(2-hydroxy-5-chlorophenyl)-2-
phenylethenylphosphine oxide (Id) was obtained via
a similar procedure. Yield 86.7%, mp 225–228°C. IR,
ν, cm–1: 764 (P–C), 1146 (P=O), 1537 (C=CAr), 1568
1
(C=CAr), 1590 (C=CAr), 3391 (OH). Н NMR (400
MHz, CDCl3), δ, ppm (J, Hz): 5.28 br.d (1Н, Н5, X of
ABX, JНСН 2.6), 6.90 d.d (1Н, Н7, A of ABX, JAX
4
4
5. Aleksandrov, V.V., Kislotnost’ nevodnych rastvorov
(Acidity of Nonaqueous Solutions), Kharkiv: Vishcha
Shkola, 1981.
3
3
2.6, JAB 8.67), 7.01 d (1Н, Н8, B of ABX, JAB 8.67),
7.18 m (2Н, Н18), 7.25 m (2Н, Н15), 7.29–7.38 m (6Н,
Н14, Н20, Н19), 7.36 (1H, Н3, JPН 19.1), 7.59 and 7.78
3
6. Preparativnaya organicheskaya khimiya (Preparative
Organic Chemistry), Vul’fson, N.S., Ed., Мoscow:
Khimiya, 1964.
two m (5H, H9, H10, H11, H12), 7.98 m (2Н, Н16), 8.04
br.d (2Н, Н21, 3JНН 8.1), 8.05 br.s (1Н, ОН). 13C NMR
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ACID-BASE AND COMPLEXING PROPERTIES
1093
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